Apparatus for particle synthesis

ABSTRACT

The present invention relates generally to an apparatus for small particle and nanoparticle synthesis. A durable particle generator capable of high temperature particle synthesis is disclosed. The particle generator is configured as to minimize susceptor degradation associated with harsh reaction conditions.

BACKGROUND

1. Field of the Invention

The present invention relates generally to an apparatus for particlesynthesis and more particularly to an apparatus capable of clean hightemperature synthesis of small particles and nanoparticles.

2. Technical Background

Over the years, there has been rapid progress in the areas ofelectronics, materials science, and nanoscale technologies resulting in,for example, smaller devices in electronics, advances in fibermanufacturing and new applications in the biotechnology field. Theability to generate increasingly smaller, cleaner and more uniformparticles is necessary in order to foster technological advances inareas which utilize small particulate matter. The development of new,efficient and adaptable ways of producing small particulate matterbecomes more and more advantageous.

The size of a particle often affects the physical and chemicalproperties of the particle or compound comprising the particle. Forexample, optical, mechanical, biochemical and catalytic properties oftenchange when a particle has cross-sectional dimensions smaller than 200nanometers (nm). When particle sizes are reduced to smaller than 200 nm,these smaller particles of an element or a compound often displayproperties that are quite different from those of larger particles ofthe same element or compound. For example, a material that iscatalytically inactive in the macroscale can behave as a very efficientcatalyst when in the form of nanoparticles.

The aforementioned particle properties are important in many technologyareas. For example, in optical fiber manufacturing, the generation ofsubstantially pure silica and germanium soot particles from impureprecursors in a particular size range (about 5-300 nm) has been key inproviding optical preforms capable of producing high purity opticalfiber. Also, in the field of pharmaceuticals, the generation ofparticles having certain predetermined properties is advantageous inorder to optimize, for example, in vivo delivery, bioavailability,stability of the pharmaceutical and physiological compatibility. Theoptical, mechanical, biochemical and catalytic properties of particlesare closely related to the size of the particles and the size of thecompounds comprising the particles. Gas-phase methods of particlegeneration are attractive, since gas-phase methods typically yield largequantities of high purity particles which are within a desirable sizerange.

Particle generators such as aerosol reactors have been developed forgas-phase nanoparticle synthesis. Examples of these aerosol reactorsinclude flame reactors, tubular furnace reactors, plasma reactors, andreactors using gas-condensation methods, laser ablation methods, andspray pyrolysis methods. In particular, hot wall tubular furnacereactors have proven adept for soot particle generation for silicapreform production in optical fiber manufacturing. Hot wall tubularfurnace reactors normally use resistive heating elements or use burnersto supply energy to reactor walls near the reaction zone.

Induction Soot Generators (ISGs) are examples of hot wall tubularfurnace reactors using inductive heating elements to heat the reactorwalls. Examples of such ISGs developed for synthesis of silica sootparticles for use in optical fiber manufacturing are described incommonly owned US Patent Application Publication 2004/0206127 thedisclosure of which is incorporated herein by reference in its entirety.The ISGs described in that reference have inductively heated reactorwalls typically made of platinum, rhodium, or a platinumrhodiumcompound. A description of one embodiment of an ISG in that referencealso shows the use of Radio Frequency (RF) electromagnetic energy toheat certain portions of the reaction zone, and mentions the possibleuse of graphite as a suitable RF susceptor. ISGs have a number ofadvantages over other tubular soot generators. For example, combustionis not needed for supplying the energy to heat the reactor walls of thereaction zone in order to support the chemical reaction. Also, there isan increased ability to control the process temperature including thereaction temperature due to the increased control of the energy sourceas compared to generators using burner heating of the walls of thereaction zone.

However, ISGs do have some disadvantages. For example, the reactor wallsof the reaction zone may become damaged due to exposure of the reactorwalls to aggressive chemicals, such as chlorine (Cl) and oxygen (O) ionsat high temperatures (above 1500° C.). These aggressive environmentalconditions are damaging even for reactor walls made from platinum,rhodium, or a platinumrhodium compound. As a result, the mechanical andinduction properties of the reactor walls deteriorate over time. Also,this degradation of the reactor wall materials allows platinum andrhodium compounds to contaminate the synthesized particles. Whendegradation occurs, the reactor wall material must be replaced, which isboth costly and time consuming. It would be advantageous to develop anapparatus capable of high temperature particle synthesis wheredegradation of the reactor walls is minimized and if any degradationoccurs, contamination would be isolated from the reaction area.

SUMMARY OF THE INVENTION

Apparatuses for generating particles are disclosed herein.

In one embodiment of the present invention, the apparatus comprises atleast one vessel having an interior space where material is heated andat least one susceptor which is capable of generating heat from energysupplied by an energy source. The susceptor is disposed such that theinterior space of the vessel is heated. The susceptor is separated fromthe interior space via a barrier layer.

In another embodiment of the present invention, the apparatus comprisesat least one susceptor which is capable of generating heat fromelectromagnetic energy in the form of microwave heating or laser heatingwhich provides energy to the susceptor thus heating the precursormaterials within the interior space. In this embodiment, the barrierlayer may be absent.

In another embodiment of the present invention, the apparatus comprisesa plurality of vessels that are connected in sequence. The interiorspace of each of the plurality of vessels is in fluid communication withthe interior space of the next vessel in sequence.

In another embodiment of the present invention, the apparatus comprisesat least one inlet for receiving material and at least one cylindricalvessel in fluid communication with the inlet having an interior spacefor accommodating reactants. The cylindrical vessel has at least onecylindrical susceptor, wherein the susceptor material is selected fromthe group consisting of platinum, rhodium, graphite, and aplatinumrhodium compound and is capable of being acted upon byelectromagnetic energy, generating heat and being disposed such thatheat is applied to the interior space. The cylindrical vessel alsocomprises a barrier layer, wherein the barrier layer material isselected from the group consisting of silica glass and quartz, encasingthe cylindrical susceptor wherein a space is present between thecylindrical susceptor and the barrier layer. An energy source is incommunication with the cylindrical vessel for providing electromagneticenergy to the cylindrical susceptor.

It would be advantageous to develop an apparatus capable of hightemperature particle synthesis where the susceptors are not exposed toaggressive environmental conditions and where the susceptors could bemade from inexpensive materials.

Additional features and advantages of the invention will be set forth inthe detailed description which follows, and in part will be readilyapparent to those skilled in the art from the description or recognizedby practicing the invention as described in the written description andclaims hereof, as well as the appended drawings.

It is to be understood that both the foregoing general description andthe following detailed description are merely exemplary of theinvention, and are intended to provide an overview or framework tounderstanding the nature and character of the invention as it isclaimed.

The accompanying drawings are included to provide a furtherunderstanding of the invention, and are incorporated in and constitute apart of this specification. The drawings illustrate one or moreembodiment(s) of the invention and together with the description serveto explain the principles and operation of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention is best understood from the following detailed descriptionwhen read with the accompanying drawing figures.

FIG. 1 is a schematic view of an apparatus for generating particlesaccording to one embodiment of the invention.

FIG. 2 is a schematic cross-sectional view of an alternative apparatusfor generating particles according to another embodiment of theinvention.

FIG. 3 is a schematic view of an apparatus for generating particlesaccording to another embodiment of the invention having vessels inseries.

FIG. 4 is an exploded schematic view of an apparatus for generatingparticles according to another embodiment of the invention havingvessels in series.

FIG. 5 is a schematic cross-sectional view of an apparatus forgenerating particles according to another embodiment of the invention.

FIG. 6 is a schematic cross-sectional view of an apparatus forgenerating particles according to another embodiment of the presentinvention.

DETAILED DESCRIPTION

As used herein:

the term “susceptor” refers to any material capable of generating heatwhen acted upon by energy from an energy source; and

the term “barrier layer” refers to a layer of material disposed inproximity to a susceptor such that the material helps to protect thesusceptor against degradation due to environmental conditions within theinterior space.

Reference will now be made in detail to the present embodiments of theinvention, examples of which are illustrated in the accompanyingdrawings. Wherever possible, the same reference numbers will be usedthroughout the drawings to refer to the same or like parts.

In the embodiment illustrated in FIG. 1, a particle generator 10 isshown having a susceptor 12 formed into a cylindrically shaped vesselcomprising an internal surface which defines an interior space 20extending generally throughout its axial length for accommodatingprecursor materials. A continuous flow path 16 goes through the interiorspace within the vessel, whereby the precursor materials can enter theinterior space, e.g., at the bottom of the susceptor, and, afterundergoing a chemical reaction resulting from the heat generated by thepresent invention, emerges from the top of the susceptor in the form ofthe desired particles. Although the particles emerge from the top of theapparatus in this embodiment, the particles could emerge from theapparatus in other orientations, for example the apparatus could also bepositioned horizontally or in other orientation optimizing particlegeneration and/or flow. The susceptor 12 is capable of absorbingincident energy and thus generating heat, and is disposed such that theheat is transferred to the interior space 20. In this embodiment, thesusceptor preferably comprises graphite. A barrier layer 14, preferablycomprising quartz, is located between the susceptor and the interiorspace. An energy source 18, shown here as an induction coil, is locatedin proximity to the vessel for providing energy to the susceptor. Otherconventional induction heating systems can be adapted to meet the needsof this embodiment of the invention.

Although the susceptor 12 is shown in FIG. 1 as being generallycylindrical, the susceptor may be of any shape or size that permits theinterior space to accommodate the required amount of precursor material,and permits the arrangement of the energy source, the susceptor ofchoice and the barrier layer to establish the desired environmentalconditions for example, a predetermined temperature range or residencetime within the interior space and thus, generate particles from theprecursor material having the desired properties.

Although the susceptor 12 shown in FIG. 1 preferably comprises graphite,susceptor materials may alternatively comprise any substantiallyelectrically conductive material such as, platinum, rhodium or aplatinum/rhodium compound such as 80/20 platinum/rhodium. The susceptormaterial should be chosen as to be capable of generating andwithstanding the appropriate amount of heat for the intendedparticle-generating reaction from energy provided by the correspondingenergy source as described below.

Although the energy source 18 shown in FIG. 1 provides energy to thesusceptor 12 via induction heating, the energy source alternatively maybe a source of electromagnetic radiation that impinges directly on thesusceptor 12, such radiation being for example, in the InfraredFrequency range, Optical Frequency range or Radio Frequency range.

An alternative energy source is shown in FIG. 5. In this embodiment theenergy source 18 is a dielectric heating system comprising water-cooledcopper electrodes connected to water-cooled copper lines 30 circulatingback to a tank circuit. The tank circuit is a combination of inductiveand capacitive components that function together as an electronicresonator and hold the particle generator at a particular frequency. Aselectrical current alternates between these components (at an angularfrequency or wavelength determined by the combined value of thecomponents), proportional “heating” is provided in the electricallyconductive or semiconductive material placed in the center of theinductor and/or proportional “heating” is provided in any “lossy”dielectric material placed between the conductive plates of thecapacitor.

An alternative energy source is shown in FIG. 6. In this embodiment amicrowave heating system comprises a magnetron as the energy source 18for distributing microwave energy within a resonant chamber 32.

A laser heating system may be used as another alternative heatingmethod. The laser source is a high power laser working in either apulsed or continuous mode, while the susceptor comprises a heatresistant and chemically nonreactive material with respect to thereaction occurring within the interior space. The laser heating systemcan be effectively used in small particle generators, such as when theflow rates and particle volume outputs are small for example, inelectronic applications and nanotechnology.

Generally, electromagnetic energy sources allow rapid and precise tuningof the temperature of the reaction within the interior space.

Although the barrier layer 14 shown in FIG. 1 is preferably quartz, thebarrier layer may alternatively comprise silica glass, alumina, ceramicor other materials suitable for protecting the susceptor fromdegradation due to exposure to heat, chemical reactants or chemicalbyproducts or mechanical abrasion.

In the embodiment shown in FIG. 2, the barrier layer 14 encases thegraphite susceptor 12 so as to form an envelope surrounding thesusceptor. A space 24 is present between the barrier layer and thesusceptor to permit expansion of the susceptor within the envelopeallowing for some coefficient of thermal expansion (CTE) mismatchesbetween the susceptor material and the barrier layer material. Thebarrier layer is hermetically sealed and its interior is evacuated. Byhaving the barrier layer completely envelop the susceptor and having theinterior volume evacuated, the susceptor is isolated not only from thechemical reactants (i.e., the precursor materials) that produce thedesired particles but also from an oxidizing atmosphere that might leadto the oxidation and/or premature degradation of the susceptor. Even ifdegradation of the susceptor occurs, the susceptor material will remaintrapped within the barrier layer envelope. For example, even if asusceptor comprising graphite is reduced to powder form due todegradation from high temperatures, the susceptor material in powderform can still provide heat to the reactant materials within theinterior space, since the susceptor material is contained within thebarrier layer envelope.

In FIG. 5 and FIG. 6, the barrier layer 14 encases the susceptor 12.Encasing of the susceptor prevents the oxidation of the susceptor andreaction of the susceptor with precursor materials at high temperatures.Without the barrier layer encasing the susceptors, the susceptor maycause arcing to the plates in the dielectric heating system or insidethe resonant chamber of the microwave heating system. Although thesusceptor 12 in FIG. 5 and FIG. 6 preferably comprises graphite,susceptor materials may alternatively comprise platinum, rhodium, aplatinum/rhodium compound such as 80/20 platinum/rhodium, ceramicmaterials, quartz and silica glass. In some embodiments such as shown inFIG. 5 and FIG. 6, when the susceptor comprises ceramic materials,quartz or silica glass, the particle generator may provide hightemperature particle synthesis without the need for a barrier layer.

Generally the barrier layer prevents direct contact of the susceptorwith environmental conditions in the interior space which may degradethe susceptor material, such as hot and aggressive chemical conditions.For example, platinum, rhodium, or a platinumrhodium compounds used assusceptor materials in vessels not having the barrier layer have thedisadvantage of pitting as Cl and O ions at high temperatures (above1500° C.) degrade the materials and deteriorate the susceptor material'sheat generating capabilities.

In the embodiments shown in FIG. 3 and FIG. 4, the particle generator isshown having a plurality of vessels 10. The plurality of vessels isconnected in sequence such that the interior space 20 of each of theplurality of vessels is in fluid communication with the interior spaceof the next vessel in sequence. As a result, the continuous flow path 16will be connected and flow through each of the plurality of vessels. Theenergy source 18 of each of the vessels is independent from each otherfor individual heating of each of the vessels.

The configuration shown in FIG. 3 and FIG. 4 allows for at least one ofthe plurality of vessels to act as a preheater for heating precursormaterial to a temperature below the temperature required for generatingthe desired particles. A temperature gradient may be imposed by aparticle generator having individual heating capabilities for each ofthe plurality of vessels. This temperature gradient could permit gradualheating of particularly sensitive and volatile materials in a verycontrolled fashion.

Further, in FIG. 4, the continuous flow path 16 in this embodiment ismade deliberately tortuous to increase the residence time of thematerials and enhance mixing, thereby yielding material with moreuniform temperature, composition, and particle size.

Openings 26 are provided into the interior space for introducingmaterial into the apparatus at locations needed to achieve the desiredparticle generation. Turbulent flow is induced by a spacer 28 which hasan interior space with a smaller volume capacity than the attachedvessels and/or by strategic placing of the openings into the interiorspace. In this embodiment, the vessels 10 are cylindrical in shape andcomprise susceptors 12 which are cylindrical in shape. The barrier layer14 encases the susceptors. Energy is supplied by an energy source 18 tothe susceptors. The energy source is a source of electromagneticradiation via induction heating of the susceptor, and the heat istransferred to the interior space 20 through the susceptor by thermalconductivity and radiation. The energy is supplied to the susceptors viaan induction coil located in proximity to the susceptor. The inductioncoil may be water-cooled via a cooling system.

Where the generation of particles occurs is dependent upon factors suchas the amount of contact of the precursor materials have with eachother, the reaction temperature needed for the reaction to occur and theresidence time during which the materials have an opportunity to react.In the case when all precursor materials are mixed together prior to thereaction generating particles, the reaction can begin at the locationwhere the necessary reaction temperature is reached, yielding vapors ofdesired particles.

In some situations, one or several of the precursor materials are addedright after the heated zone, the reaction can start there, at atemperature lower than the maximum temperature achievable in theinterior space of the vessel. The subsequent cooling of this gas causesthe vapor of the resulting material to nucleate and condense, formingaerosol particles. This nucleation is a result of molecules colliding,escaping (evaporating) and agglomerating until a critical nucleus sizeis reached and a particle is formed. The particle sizes are typically inthe range between several nanometers and hundreds of nanometers,provided the conditions for particle agglomeration exist, for example,high enough concentration of aerosol monomers.

This plurality of vessels approach can be used for the generation ofmultilayered particles. For example, if a first aerosol material hashigh enough vapor pressure and is chemically inert with respect to theenvironmental conditions needed to form a second aerosol material, thefirst aerosol material can be injected into the interior space at anylocation along the continuous flow path of the particle generatorsimultaneously with other precursor materials so as to form amultilayered particle.

The particle generator of the present invention has the advantage ofoperating temperature capabilities at least up to about 1650° C. inaggressive chemical reactions involving halides without the problemsassociated with susceptor degradation effects associated with otherparticle generators, since there is a barrier layer between the at leaston susceptor and the interior space. Reaction conditions similar tothose described for soot particle generation in US Patent ApplicationPublication 2004/0206127 could be withstood without problems associatedwith susceptor degradation.

In the present invention, the temperature capability of the vessel islimited only by the heat resistance of the barrier layer of choice. Forexample, a barrier layer comprising quartz or comprising silica glasscould provide heat resistance for temperatures up to 2000° C. in theinterior space. This temperature may be even greater if an inert carriergas such as helium is used. Using an inert carrier gas enables operationeven at the softening temperature of the barrier material. In someapplications, other carrier gases such as argon and nitrogen may beused. The ability to use inexpensive susceptor materials is provided bythe susceptor material being separated by the barrier layer fromconditions in the interior space which may be harsh depending ontemperature and chemical interactions. For example, a particle generatorof the present invention having susceptors separated from the interiorspace by a quartz barrier layer may have susceptors made frominexpensive materials for example, graphite.

As a result, particle synthesis processes can be run very cleanly,without contamination by susceptor decomposition products, hydrocarboncombustion products and/or the presence of oxidizing species andimpurities in the interior space. For example, a particle generator ofthe present invention comprising at least one vessel comprisingsusceptors separated from the interior space by being encased by anevacuated quartz barrier layer may utilize susceptors made from aninexpensive material, even if that material is susceptible todegradation or susceptible to outgassing. Even in the case where thereis a space between the susceptor and the barrier layer which is notevacuated, susceptor degradation byproducts will be trapped in theencasing barrier layer. An evacuated space between the barrier layer andthe susceptor helps to maintain the integrity of the susceptor material,even if mechanical degradation of the susceptor occurs. In theembodiments shown in FIG. 3 and FIG. 4, susceptors comprising tungsten,iron, or other substantially conductive materials, even in liquid formupon heating, can function to provide heat to the interior space. It ispreferable to have the susceptor material be stable at high temperaturesand able to generate heat upon being acted upon by energy from theenergy source.

As a result, a wide spectrum of gas-phase chemical reactions can be usedfor high purity particle forming, including oxidation (e.g., formingparticles of oxides), reduction (e.g., forming pure metal particles, aswell as those consisting of nitrides and carbides), combination anddecomposition, and physical reactions such as vaporization andcondensation, as well as their combinations.

For the reasons mentioned above, the particle generator of the presentinvention has advantages over other particle generators, including ISGsand other tubular generators. Because of the barrier layer and/oralternative electromagnetic energy sources, the present inventionpermits the use of inexpensive susceptor materials, such as graphiteand/or fused silica. Because hot reactants contact only the barrierlayer, contamination of the produced particles by products of susceptordecomposition is minimized. As a result, it is possible to run cleanerparticle synthesis processes at high temperatures with a harsh chemicalenvironment and/or abrasive environment. Also, corrosion of thesusceptor is minimized, thus deterioration of the susceptor's mechanicaland heat generating properties are minimized.

It will be apparent to those skilled in the art that variousmodifications and variations can be made to the present inventionwithout departing from the spirit or scope of the invention. Thus, it isintended that the present invention cover the modifications andvariations of this invention provided they come within the scope of theappended claims and their equivalents.

1. A particle generator comprising at least one vessel comprising: (a)an interior space for accommodating the passage of reactant materialtherethrough, (b) at least one susceptor capable of generating heat whenacted upon by energy and being disposed such that a temperaturesufficient to heat the reactant material within a predetermined range isachieved within the interior space; and (c) a heat-transmitting barrierlayer interposed between said susceptor and the interior space forisolating said susceptor from the reactant material.
 2. The particlegenerator of claim 1 further comprising at least one energy source forproviding the energy to said susceptor.
 3. The particle generator ofclaim 2 wherein said energy source is a source of electromagneticradiation.
 4. The particle generator of claim 3 wherein the source ofelectromagnetic radiation is an induction heating system.
 5. Theparticle generator of claim 3 wherein the source of electromagneticradiation is a dielectric heating system.
 6. The particle generator ofclaim 3 wherein the source of electromagnetic radiation is a microwaveheating system.
 7. The particle generator of claim 1 wherein thesusceptor is selected from the group consisting of molybdenum, platinum,rhodium, graphite and a platinumrhodium compound.
 8. The particlegenerator of claim 1 wherein the barrier layer comprises a materialwhich is nonreactive with respect to the reactant material.
 9. Theparticle generator of claim 1 wherein the barrier layer comprisesquartz.
 10. The particle generator of claim 1 wherein the barrier layercomprises silica glass.
 11. The particle generator of claim 1 whereinthe barrier layer comprises a ceramic material.
 12. The particlegenerator of claim 1 wherein the barrier layer encases said susceptor.13. The particle generator of claim 12 wherein the susceptor is selectedfrom the group consisting of ceramic materials, quartz, silica glass,molybdenum, platinum, rhodium, graphite and a platinumrhodium compound.14. The particle generator of claim 12 wherein an evacuated space ispresent between the barrier layer and said susceptor.
 15. The particlegenerator of claim 1 further comprising a plurality of vessels providinga continuous flow path wherein the plurality of vessels are connected insequence such that the interior space of each of the plurality ofvessels is in fluid communication with the interior space of the nextvessel in sequence.
 16. The particle generator of claim 15 wherein saidcontinuous flow path is disposed such that turbulent flow causes mixingof the material in at least one of the plurality of vessels.
 17. Theparticle generator of claim 15 wherein said energy source of each of theplurality of vessels is independent from each other for individualheating of each of the vessels.
 18. The particle generator of claim 15wherein at least one of the plurality of vessels is a preheater forheating material to a temperature less than the temperature required forparticle generation.
 19. The particle generator of claim 15 furthercomprising at least one inlet transversing the barrier layer forintroducing precursor materials at a desired location along thecontinuous flow path.
 20. A particle generator comprising: at least onecylindrical vessel comprising an interior space for accommodatingprecursor materials; at least one inlet for receiving precursormaterials in fluid communication with said cylindrical vessel; at leastone cylindrical susceptor, wherein said susceptor is selected from thegroup consisting of platinum, rhodium, graphite, and a platinumrhodiumcompound, capable of being acted upon by electromagnetic energy,generating heat and being disposed such that a temperature sufficient toheat the reactant material within a predetermined range is achievedwithin the interior space; a barrier layer, wherein the barrier layer isselected from the group consisting of silica glass and quartz, encasingsaid susceptor wherein an evacuated space is present between saidsusceptor and the barrier layer; and an energy source in communicationwith said cylindrical vessel for providing electromagnetic energy tosaid susceptor.
 21. A particle generator comprising at least one vesselcomprising: (a) an interior space for accommodating the passage ofreactant material therethrough; (b) at least one susceptor selected fromthe group consisting of ceramic materials, quartz, silica glass,molybdenum, platinum, rhodium, graphite and a platinumrhodium compoundcapable of generating heat when acted upon by electromagnetic energyfrom a corresponding energy source and being disposed such that atemperature sufficient to heat the reactant material within apredetermined range is achieved within the interior space; and (c) atleast one energy source for providing the electromagnetic energy to saidsusceptor wherein the energy source is selected from the groupconsisting of a microwave heating system and a laser heating system.